US4835233A - Liquid polymerizable compositions for the production of substitutes for optical glasses - Google Patents

Liquid polymerizable compositions for the production of substitutes for optical glasses Download PDF

Info

Publication number
US4835233A
US4835233A US07/237,664 US23766488A US4835233A US 4835233 A US4835233 A US 4835233A US 23766488 A US23766488 A US 23766488A US 4835233 A US4835233 A US 4835233A
Authority
US
United States
Prior art keywords
weight
diethylene glycol
tris
bis
allylcarbonate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US07/237,664
Other languages
English (en)
Inventor
Fiorenzo Renzi
Franco Rivetti
Ugo Romano
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ENICHEM SYNTHESIS SpA AN ITALIAN Co OF PALERMO ITALY
Original Assignee
Enichem Sintesi SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Enichem Sintesi SpA filed Critical Enichem Sintesi SpA
Application granted granted Critical
Publication of US4835233A publication Critical patent/US4835233A/en
Assigned to ENICHEM SYNTHESIS S.P.A., AN ITALIAN COMPANY OF PALERMO, ITALY reassignment ENICHEM SYNTHESIS S.P.A., AN ITALIAN COMPANY OF PALERMO, ITALY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: ENICHEM SINTESI S.P.A.
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/24—Esters of carbonic or haloformic acids, e.g. allyl carbonate

Definitions

  • the present invention relates to an allylcarbonates-based liquid composition, which can be converted into optical articles, by the casting technology and with fast hardening cycle.
  • the products are interesting which derive from the polymerization of glycol bis(allylcarbonates), and in particular of diethylene glycol bis(allylcarbionate), and this in view of the optical and mechanical characteristics of the related polymerization products, which are hence used in manufacturing sheets and ophthalmic and safety lenses.
  • the subject optical articles are usually prepared by the casting technology, by polymerizing mixtures containing diethylene glycol bis(allyl carbonate) and a free-radical initiator, inside a glass mould having a shape corresponding to that of the article which one wants to produce.
  • liquid, polymerizable compositions which contain diethylene glycol bis(allyl carbonate), and are capable of being cast, with low volume shrinking, producing optical articles endowed with improved characteristics, in particular as relates to the impact strength.
  • compositions are disclosed in the U.S. patent application Ser. No. 863.526 filed on May 15, 1986, in the same Applicant's name.
  • this composition which is formed by bis(allylcarbonate) of monomer and oligomer diethylene glycol, besides by a monomer of tris(hydroxyethyl)isocyanurate tris(allylcarbonate), shows the additional advantage of a good fluidity under the ambient conditions, which makes it easier to be handled during the casting process.
  • the present invention relates to a composition containing diethylene glycol bis(allyl carbonate), fluid under the ambient conditions and polymerizable by short polymerization cycles to optical articles having good optical and mechanical characteristics, formed by:
  • composition containing furthermore at least a free-radical polymerization initiator, in an amount of from 1 to 6% by weight, relatively to the total of the weights of (A), (B), (C) and (D) components.
  • the (A) component of the liquid, polymerizable composition of the present invention is bis(allylcarbonate) of monomer diethylene glycol, having the formula ##STR2## wherein R is the radical of diethylene glycol.
  • This component can be prepared by means of the reaction of diallylcarbonate with diethylene glycol, in a molar ratio to each other equal to or higher than about 10/1, by working in the presence of a basic catalyst, e.g., according to as disclosed in European patent application publ. No. 35,304. Under these conditions, a reaction product is obtained, which is constituted by at least 80-90% by weight by compound (I), the balance to 100% being constituted by oligomers of diethylene glycol bis(allylcarbonate).
  • the component (A) of the polymerizable, liquid composition can be constituted by the compound (I) alone, or by a mixture containing at least about 80-90% by weight of compound (I), the balance to 100% being constituted by its oligomers.
  • the component (A) is present in the liquid, polymerizable composition in an amount of from 10 to 35% by weight.
  • the (B) component of the liquid, polymerizable composition of the present invention is an oligomer or a mixture of oligomers of bis(allylcarbonate) of diethylene glycol, definable by the formula: ##STR3## wherein R is the radical of diethylene glycol, and n has a value, or an average value, comprised between the range of from 2 to 5.
  • This component can be prepared by reacting diallylcarbonate with diethylene glycol, in a molar ratio to each other of the order of about 2/1, by operating in the presence of a basic catalyst, in a similar way to as for above (A) component.
  • an essentially oligomeric reaction product which corresponds to the above formula (II), with an average value of n of the order of 3, and is constituted by about 60-70% by weight by oligiomers, the balance to 100% being constituted by bis(allylcarbonate) of monomer diethylene glycol.
  • the (B) component is present in an amount of from 25 to 50% by weight.
  • the (C) component of the liquid, polymerizable composition of the present invention is tris(allylcarbonate) of monomer tris(hydroxyethyl)isocyanurate, to be defined by the formula: ##STR4##
  • This component can be prepared by reacting diallylcarbonate with tris(hydroxyethyl)isocyanurate, in a molar ratio to each other higher than about 10/1, by operating in the presence of a basic catalyst, in a similar way as for the above (A) component.
  • reaction product which is constituted by at least 60-70%by weight of compound (III), the balance to 100% being constituted by oligomers of tris(hydroxyethylisocyanurate) tris(allylcarbonate).
  • the (C) component of the liquid, polymerizable composition can be constituted by component (III) only, or it can be constituted by a mixture containing at least about 60-70% by weight of component (III), the balance to 100% being constituted by its oligomers.
  • the (C) component is present in the liquid, polymerizable composition in an amount of from 20 to 35% by weight.
  • the (D) component of the liquid, polymerizable composition of the present invention is an unsaturated, monofunctional vinyl or methacryl ester monomer, generally selected from vinyl acetate and methyl methacrylate which, in the preferred form of practical embodiment, is present in the composition in an amount of from 5 to 20% by weight.
  • the liquid, polymerizable composition of the present invention contains furthermore one or more polymerization initiators, soluble in the same composition, and capable to generate free radicals within a temperature range of from 30° to about 100° C.
  • polymerization initiators are diisopropylperoxydicarbonate, dicyclohexylperoxydicarbonate, di-sec-butylperoxydicarbonate, dibenzoylperoxide and tert-butylperbenzoate.
  • the polymerization initiator in present in an amount of from 2 to 5% by weight, relatively to the total of the weights of (A), (B), (C) and (D) components.
  • the liquid, polymerizable composition of the present invention may additionally contain one or more conventional additive(s), such as stabilizers, release agents, dyes, pigments, UV-light or IR-light absorbers, and the like, however in a total amount not higher than 1% by weight relatively to the total of the weights of (A), (B), (C) and (D) components.
  • additives such as stabilizers, release agents, dyes, pigments, UV-light or IR-light absorbers, and the like, however in a total amount not higher than 1% by weight relatively to the total of the weights of (A), (B), (C) and (D) components.
  • the liquid, polymerizable composition of the present invention is fluid under ambient conditions, and is transformed, by means of the casting process, into such optical articles as sheets, ophthalmic and safety lenses.
  • the polymerization is initiated by free radicals, generated by the decomposition of the polymerization initiators present in the same composition, by generally operating at temperatures of from 40° to 100° C.
  • the times necessary for the complete polymerization of the composition are comprised within the range of from 1 to 5 hours, in particular as a function of the shape and of the dimensions of the article to be manufactured, with neither composition prepolymerization treatments, nor post-treatments of the manufactured article after the mould opening being required.
  • the polymerization occurs with reduced shrinking phenomena, and the obtained articles show a whole of particularly favourable optical and mechanical properties, as well as the complete absence of the typical faults, peculiar of the articles manufactured by starting from the compositions of the prior art, when said known compositions are submitted to accelerated polymerization cycles.
  • (A) bis(allylcarbonate) of monomer diethylene glycol reaction product of diallylcarbonate with diethylene glycol, in a molar ratio to each other of 12/1, by operating according to as disclosed in European patent application publ. No. 35,304.
  • This product contains about 85-90% by weight of bis(allylcarbonate) of diethylene glycol (I), the balance to 100% being constituted by oligomers thereof;
  • the (A), (B), (C) and (D) components are mixed in the hereunder shown ratios, and dicyclohexylperoxydicarbonate (DCPC) is then added to their mixture, at a constant concentration of 4% by weight relatively to the same composition.
  • DCPC dicyclohexylperoxydicarbonate
  • compositions By said composition, different types of lenses are prepared, by pouring into and polymerization inside such glass moulds, as customary used in the industrial practice.
  • the polymerization of the composition is carried out in a temperature-controlled water bath, by variable time-temperature cycles, according to the type of lens being manufactured.
  • composition 1 A liquid, polymerizable composition according to the invention (composition 1) and two comparison polymerizable compositions (compositions 2 and 3) according to the prior art are prepared, as reported in Table 1.
  • the viscosity of the three compositions, in the absence of DCPD, is respectively of 28, 14 and 83 centistokes, at the temperature of 25° C.
  • neutral lenses of 1.8 mm in thickness and 75 mm in diameter are prepared, by polymerization according to the time-temperature cycle as shown in FIG. 1.
  • the same compositions are polymerized by a cycle of 72 hours at 48° C., followed by two hours at 110° C. (for the post-crosslinking), under which conditions the polymerized materials reach their highest conversion degree.
  • Rockwell (M) hardness as measured by the Rockwell durometer, at lens centre (ASTM D-785);
  • Yellow index (YI(, defined as: ##EQU1## as determined by the Gardner XL805 colorimeter (ASTM D-1925) Haze (%) and visible transmittance (%), as measured by the Gardner XL-211 Hazegard (ASTM D-1003).
  • composition 1 of Example 1 two neutral lenses of 1.8 mm in thickness, and 75 mm in diameter, are prepared, by carrying out the polymerization by two different time-temperature cycles--(a) and (b) cycle--each cycle having an overall duration of two hours, according to the pattern as shown in FIG. 2.
  • Example 1 With the composition of Example 1, two finished, respectively +0.25 and +2.0 lenses of 70 mm in diameter are prepared, by means of the two time-temperature cycles as used in foregoing Example 2.
  • composition 1 of Example 1 three semifinished, bifocal lenses, with basic curvature of respectively 4.25; 6.25; and 8.25; and of 70 mm in diameter are prepared, by operating by a three-hours polymerization cycle, having the pattern as shown in FIG. 3.
  • composition 4 A liquid, polymerizable composition (composition 4) is prepared, from:
  • the viscosity of the composition in the absence of DCPD, is of 29 centistokes at 25° C.
  • a neutral lens of 1.8 mm in thickness and 75 mm in diameter, and two finished, respectively +0.25 and +2.0 lenses, of 70 mm in diameter are prepared, by using the (b) polymerization cycle of Example 2, having the overall duration of 2 hours.
  • lenses are prepared from the same composition, by a polymerization cycle of 72 hours at 48° C., followed by two hours at 110° C. All of the lenses result free from faults and have the hardness values as shown in Table 6.
  • the obtained lenses are free from faults and have the hardness values as shown in Table 7.
  • a set of finished lenses are prepared by means of the polymerization cycle of 1.5 hours of duration as shown in FIG. 5, by starting from the polymerizable liquid compositions as reported in Table 8.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Eyeglasses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US07/237,664 1985-12-19 1988-08-25 Liquid polymerizable compositions for the production of substitutes for optical glasses Expired - Fee Related US4835233A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT23289A/85 1985-12-19
IT8523289A IT1207518B (it) 1985-12-19 1985-12-19 Composizione liquida e polimerizzabile per la produzionedi sostituiti di vetri ottici.

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US06942381 Continuation 1986-12-16

Publications (1)

Publication Number Publication Date
US4835233A true US4835233A (en) 1989-05-30

Family

ID=11205697

Family Applications (1)

Application Number Title Priority Date Filing Date
US07/237,664 Expired - Fee Related US4835233A (en) 1985-12-19 1988-08-25 Liquid polymerizable compositions for the production of substitutes for optical glasses

Country Status (10)

Country Link
US (1) US4835233A (de)
EP (1) EP0227178A3 (de)
JP (1) JPH0627161B2 (de)
CA (1) CA1268287A (de)
CS (1) CS274286B2 (de)
DD (1) DD254015A5 (de)
DK (1) DK609786A (de)
IE (1) IE863291L (de)
IT (1) IT1207518B (de)
NO (1) NO166795C (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5128384A (en) * 1988-06-17 1992-07-07 Enichem Synthesis S.P.A. Process for preparing organic glasses
US5237029A (en) * 1991-04-03 1993-08-17 Takemoto Yushi Kabushiki Kaisha Polymerizable molding liquid resins, compositions containing same and in-mold cured products therefrom
US5952441A (en) * 1997-12-30 1999-09-14 Ppg Industries Ohio, Inc. Partially polymerized mixture of diethylene glycol (allyl carbonate) compounds
AU764148B2 (en) * 1999-12-13 2003-08-14 Ppg Industries Ohio, Inc. Polymerizable polyol(allyl carbonate) compositions
US20030173551A1 (en) * 1999-12-13 2003-09-18 Nagpal Vidhu J. Polymerizable polyol (allyl carbonate) compositions
US11028206B2 (en) 2016-08-16 2021-06-08 Ppg Industries Ohio, Inc. Polymerizable composition for optical articles

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1228546B (it) * 1987-07-31 1991-06-20 Enichem Sintesi Composizione liquida polimerizzabile in vetri organici dotati di elevata stabilita' termica
IT1223527B (it) * 1987-12-18 1990-09-19 Enichem Sintesi Composizione liquida polimerizzabile in vetri organici dotati di basso assorbimento d'acqua e di elevata stabilita' termica
IT1245384B (it) * 1991-03-28 1994-09-20 Enichem Sintesi Vetro organico con resistenza all'urto migliorata e con indice di rifrazione pari o simile a quello del vetro minerale
US5286816A (en) * 1991-03-28 1994-02-15 Enichem Synthesis S.P.A. Organic glass with improved impact strength and with a refractive index equal or similar to that of mineral glass
US5237032A (en) * 1992-09-30 1993-08-17 Istituto Guido Donegani S.P.A. Microwave processing of carbonate monomers

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3658801A (en) * 1969-06-10 1972-04-25 Dart Ind Inc Trisubstituted isocyanurates
US4205154A (en) * 1977-10-05 1980-05-27 Ppg Industries, Inc. Triallyl carbonate polymers
JPS5661412A (en) * 1979-10-25 1981-05-26 Hoya Corp High refractive-index terpolymer
US4521577A (en) * 1983-01-13 1985-06-04 Enichimica S.P.A. Liquid polymerizable compositions of a carbonate oligomer, an allylcarbonate and vinyl acetate
US4622376A (en) * 1985-06-27 1986-11-11 Ppg Industries, Inc. Composition of aromatic poly(allylcarbonate), styrene materials, and crosslinker containing three or more ethylenically unsaturated groups for producing polymer of high refractive index and low yellowness
US4623708A (en) * 1985-03-01 1986-11-18 Coburn Optical Industries, Inc. Prepolymerization of monomer compositions containing diethylene glycol bis(allyl carbonate)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1129688A (en) * 1965-10-29 1968-10-09 Bausch & Lomb Diethylene glycol bis (allyl carbonate) terpolymer

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3658801A (en) * 1969-06-10 1972-04-25 Dart Ind Inc Trisubstituted isocyanurates
US4205154A (en) * 1977-10-05 1980-05-27 Ppg Industries, Inc. Triallyl carbonate polymers
JPS5661412A (en) * 1979-10-25 1981-05-26 Hoya Corp High refractive-index terpolymer
US4521577A (en) * 1983-01-13 1985-06-04 Enichimica S.P.A. Liquid polymerizable compositions of a carbonate oligomer, an allylcarbonate and vinyl acetate
US4623708A (en) * 1985-03-01 1986-11-18 Coburn Optical Industries, Inc. Prepolymerization of monomer compositions containing diethylene glycol bis(allyl carbonate)
US4622376A (en) * 1985-06-27 1986-11-11 Ppg Industries, Inc. Composition of aromatic poly(allylcarbonate), styrene materials, and crosslinker containing three or more ethylenically unsaturated groups for producing polymer of high refractive index and low yellowness

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5128384A (en) * 1988-06-17 1992-07-07 Enichem Synthesis S.P.A. Process for preparing organic glasses
US5237029A (en) * 1991-04-03 1993-08-17 Takemoto Yushi Kabushiki Kaisha Polymerizable molding liquid resins, compositions containing same and in-mold cured products therefrom
US5952441A (en) * 1997-12-30 1999-09-14 Ppg Industries Ohio, Inc. Partially polymerized mixture of diethylene glycol (allyl carbonate) compounds
AU764148B2 (en) * 1999-12-13 2003-08-14 Ppg Industries Ohio, Inc. Polymerizable polyol(allyl carbonate) compositions
US20030173551A1 (en) * 1999-12-13 2003-09-18 Nagpal Vidhu J. Polymerizable polyol (allyl carbonate) compositions
US7214754B2 (en) 1999-12-13 2007-05-08 Ppg Industries Ohio, Inc. Polymerizable polyol (allyl carbonate) compositions
AU764148C (en) * 1999-12-13 2007-11-15 Ppg Industries Ohio, Inc. Polymerizable polyol(allyl carbonate) compositions
US11028206B2 (en) 2016-08-16 2021-06-08 Ppg Industries Ohio, Inc. Polymerizable composition for optical articles

Also Published As

Publication number Publication date
NO865116L (no) 1987-06-22
JPH0627161B2 (ja) 1994-04-13
CS960786A2 (en) 1990-08-14
CA1268287A (en) 1990-04-24
IT8523289A0 (it) 1985-12-19
DK609786D0 (da) 1986-12-17
IT1207518B (it) 1989-05-25
NO166795C (no) 1991-09-04
JPS62156113A (ja) 1987-07-11
NO865116D0 (no) 1986-12-17
EP0227178A3 (de) 1988-12-21
DD254015A5 (de) 1988-02-10
NO166795B (no) 1991-05-27
IE863291L (en) 1987-06-19
DK609786A (da) 1987-06-20
CS274286B2 (en) 1991-04-11
EP0227178A2 (de) 1987-07-01

Similar Documents

Publication Publication Date Title
EP0114080B1 (de) Polymerisierbare flüssige Zusammensetzung anwendbar für die Herstellung von Polymeren mit hervorragenden optischen und mechanischen Eigenschaften, aus dieser Zusammensetzung erhaltene Polymere und Gegenstände
US4812545A (en) Process for the preparation of substitutes for optical glasses and polymerizable liquid composition suitable to that purpose
US4835233A (en) Liquid polymerizable compositions for the production of substitutes for optical glasses
IE913269A1 (en) Copolymerization process and optical copolymer produced therefrom
KR910008606B1 (ko) 고굴절율 광학물품의 제조용 액체의 중합조성물
KR20200065102A (ko) 알릴 카르보네이트 단량체에 기반한 중합성 조성물, 상기 조성물로부터 수득가능한 중합된 생성물 및 그의 용도
KR920009619B1 (ko) 유기유리 제조방법
US5173552A (en) Process for the production of thermoformed articles by polymerizing compositions comprising diethylene glycol bis (allylcarbonate)
EP0204083B1 (de) Verfahren zur Herstellung von in der Wärme umgeformten Gegenständen
US4959433A (en) Partially polymerized bis(allylic carbonate) monomer having high allylic utilization
EP0241997B1 (de) Flüssige und polymerisierbare Zusammensetzung für die Herstellung organischer Gläser mit hoher Abriebfestigkeit
WO2000031584A2 (en) Liquid composition polymerizable into organic glasses with a high refractive index
IL103342A (en) Copolymers containing propylene and contact lenses made from them
US5204430A (en) Liquid polymerizable composition for the production of high refractive index optical articles
KR900007767B1 (ko) 고마모강도의 유기질 안경제조방법
EP0329799B1 (de) Zum Teil polymerisiertes bis(Allylcarbonat)monomer mit hoher allylischer Ausnutzung
JPH0284409A (ja) 重合可能な液状組成物
JPS62116615A (ja) 透明樹脂成型体の製造方法
JPH0672961B2 (ja) 光学用樹脂およびその製造法

Legal Events

Date Code Title Description
AS Assignment

Owner name: ENICHEM SYNTHESIS S.P.A., AN ITALIAN COMPANY OF PA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:ENICHEM SINTESI S.P.A.;REEL/FRAME:005142/0238

Effective date: 19880831

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Lapsed due to failure to pay maintenance fee

Effective date: 19970604

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362